CN109817892B - A kind of method of copper current collector making Nano surface - Google Patents
A kind of method of copper current collector making Nano surface Download PDFInfo
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- CN109817892B CN109817892B CN201910168481.XA CN201910168481A CN109817892B CN 109817892 B CN109817892 B CN 109817892B CN 201910168481 A CN201910168481 A CN 201910168481A CN 109817892 B CN109817892 B CN 109817892B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to field of lithium ion battery more particularly to a kind of methods of copper current collector making Nano surface.The described method includes: 1) corrode Copper substrate preparation and pre- matrix；2) pre- matrix reduction prepares foraminous die plate；3) the standby activation template of position activity made of metal；4) presoma is prepared using Anodic Stripping principle；5) calcining preparation surface is deposited with active metal and carbon and forms the copper current collector of nanostructure.The method of the present invention is simple, and repeatability is strong, and controllability is good；Three-dimensional manometer copper electrochemically inertia and stable structure；The structure of three-dimensional manometer copper is by the diffusion admittance for greatly reducing lithium ion and reduces polarization, can largely promote cycle performance and high rate performance；By position activity metallic element and the specific surface area for further increasing its nanostructure, the chemical property of electrode material is made to be further improved；Negative electrode material obtained by the method for the present invention improves the specific capacity of battery without using binder and conductive agent.
Description
Technical field
The present invention relates to field of lithium ion battery more particularly to a kind of methods of copper current collector making Nano surface.
Background technique
Lithium ion battery have operating voltage height, height ratio capacity, have a safety feature, with environment compatibility by force, do not remember
The advantages that effect, operating temperature range are wide, self discharge is smaller and has extended cycle life is widely used in computer, portable at present
Formula electronic equipment, electric car, medical technology, national defense industry, the even key areas such as aerospace.
Main negative electrode material is carbon material currently on the market, and graphite possesses higher specific capacity, suitable charging potential
Distribution, amount the advantages that multivalence is honest and clean and the actual capacity of 300 ~ 330 mAh/g, but the theoretical peak of its first charge-discharge efficiency limits
System and irreversible capacitance loss constrain its further development.
And ferroso-ferric oxide, tin oxide, zirconium oxide etc. have higher specific capacity, i.e. storage lithium energy relative to graphite type material
Power is stronger.Therefore when researching and developing high performance negative electrode material, these are exactly the favorite of researcher.But it bears on a current collector
After the active material for carrying high capacity, the dusting, mistake of caused volume change and active material during charge and discharge cycles
Effect is the huge problem to be faced.
Summary of the invention
Volume change, active matter are easy to produce to solve existing lithium ion battery negative material after improving storage lithium ability
The problems such as dusting and failure of matter, the present invention provides a kind of methods of copper current collector making Nano surface.It will realize following several
A purpose: 3-D nano, structure is prepared on copper current collector surface first, to realize；Second, realizing the alloy of 3-D nano, structure
Change；Third, realizing effective buffers active substance in lithium ion abjection telescopiny using composition metal 3-D nano, structure
Volume change improves the cyclical stability of lithium battery and the purpose of high rate performance.
To achieve the above object, the present invention uses following technical scheme.
A kind of method of copper current collector making Nano surface, the described method comprises the following steps:
1) alkalies is configured, will be placed in alkalies by pretreated Copper substrate and erode processing, after erosion
It is dried, pre- matrix is obtained；
2) using pre- matrix as working electrode, platinum or graphite as, as reference electrode, being set to electrode, saturated calomel electrode
Pre- matrix is restored using three-electrode system in electrolyte, forms foraminous die plate；
3) prepare the electrodeposit liquid containing active metallic ion, using foraminous die plate as working electrode, platinum or graphite as
To electrode, saturated calomel electrode as reference electrode, it is placed in electrodeposit liquid and utilizes three-electrode system in the hole of foraminous die plate
Middle position activity metal oxide obtains activation template；
4) prepare organic liquor, using activate template as anode, using platinum or graphite as cathode, using organic liquor as electrolyte,
It is electrolysed using Anodic Stripping principle, grows villiform nanostructure in activation template surface to get presoma is arrived；
5) presoma is placed in protective atmosphere and is calcined, surface can be obtained and be deposited with active metal and carbon and form nanometer
The copper current collector of structure.
The present invention passes through the collector of building 3-D nano, structure first, and deposits transition metal oxide on this basis
Isoreactivity substance, with the volume change of active material in the own space buffer charge and discharge process of three-dimensional collector.In addition, this method
Advantage also reside in it and do not need binder and conductive agent.And on this basis, using Anodic Stripping principle, so that the three of building
Dimension nanometer construction Copper substrate further realizes villiform nanostructure, further increases its specific surface area, and storage lithium ability obtains
It is further to be promoted, there is the chemical property more having.
Preferably, alkalies described in step 1) is formulated by strong oxidizer, highly basic and water, wherein strong oxidizer
Concentration is 0.05~2mol/L, and the concentration of highly basic is 1~5mol/L；The drying process temperature is 150~250 DEG C, the time 1
~3h；The strong oxidizer includes potassium peroxydisulfate, potassium bichromate and potassium permanganate.It can be in Copper substrate using the lye of the proportion
Surface erosion goes out three-dimensional network shape nanostructure, and compared to copper base, specific surface area is greatly improved.
Preferably, electrolyte described in step 2 is the potassium sulfate of 0.5~2mol/L or the sodium sulphate water of 0.5~2mol/L
Solution.
Preferably, reduction potential is -0.1~-3V when restoring described in step 2, the recovery time is 100~1000s.
Cupric can be quickly reduced to metallic copper under the conditions of the reduction potential, and retain its three-dimensional network abundant
Shape nanostructure.
Preferably, active metallic ion described in step 3) include iron ion, zinc ion, titanium ion, nickel ion and cobalt from
Son.
The reactive metal oxides that above several active metallic ions are prepared all have high specific capacity, can be right
The electrochemistry of negative electrode material, which is able to achieve, significantly to be optimized.
Preferably, the preparation method of electrodeposit liquid described in step 3) are as follows: the sulfate containing active metallic ion to be dissolved in
In water, highly basic is added and stirs, it is electrodeposit liquid that supernatant is then taken after 10~14h of standing；Wherein, sulfate concentration is
0.05~2mol/L, strong base concentrations are 1~5mol/L.
Preferably, electrodeposition condition described in step 3) are as follows: electro-deposition electric current is -5~-20mA/cm2, electrodeposition time
For 20~100s.
It can be realized preferably electrodeposition effect under the electrodeposition condition.
Preferably, organic liquor described in step 4) is the DMF solution containing 0.2~0.8mol/L isonicotinic acid.
The organic liquor can promote the copper ion of Anodic Stripping to be further attached to matrix surface, and then form villiform and receive
Rice structure.
Preferably, the condition of electrolysis described in step 4) are as follows: decomposition voltage is 3.0~4.5V, 15~20min of time.
Anodic Stripping process control is strong under the electrolytic condition, and the villiform nanostructure of formation is intensive and uniform.
Preferably, calcination temperature is 600~800 DEG C in calcination process described in step 5), calcination time is 2~5h.
The beneficial effects of the present invention are:
1) present invention prepares 3-D nano, structure cathode, and method is simple, and repeatability is strong, and controllability is good, prepared surface
Being deposited with active metal and carbon and form the copper current collector of nanostructure can direct-assembling battery；
2) the three-dimensional manometer copper obtained through redox electrochemically inertia and stable structure, can provide expansion space and
Stable electrical contact, the swelling stress facilitated in charge and discharge process discharge, it can be achieved that battery capacity is obviously improved；
3) structure of three-dimensional manometer copper by the diffusion admittance for greatly reducing lithium ion and reduces polarization, can be largely
Promote cycle performance and high rate performance；
4) by position activity metallic element and the specific surface area for further increasing its nanostructure, make the electricity of electrode material
Chemical property is further improved；
5) negative electrode material obtained by the method for the present invention improves the specific volume of battery without using binder and conductive agent
Amount.
Detailed description of the invention
Fig. 1 is that the SEM of three-dimensional manometer copper oxide schemes；
Fig. 2 is that the SEM of three-dimensional manometer Copper substrate schemes；
Fig. 3 is that the SEM of villiform nanostructure schemes.
Specific embodiment
Further clear detailed description explanation is made to the present invention below in conjunction with specific embodiment and Figure of description.This
Field those of ordinary skill will realize the present invention based on these explanations.In addition, being related in following the description
The embodiment of the present invention be generally only an of the invention branch embodiment, instead of all the embodiments.Therefore, it is based on this hair
Embodiment in bright, those of ordinary skill in the art's every other reality obtained without making creative work
Example is applied, should fall within the scope of the present invention.
Examples 1 to 5
A kind of method of copper current collector making Nano surface, the described method comprises the following steps:
1) alkalies is configured, will be placed in alkalies by pretreated Copper substrate and erode processing, after erosion
It is dried, pre- matrix is obtained；
2) using pre- matrix as working electrode, platinum or graphite as, as reference electrode, being set to electrode, saturated calomel electrode
Pre- matrix is restored using three-electrode system in electrolyte, forms foraminous die plate；
3) prepare the electrodeposit liquid containing active metallic ion, using foraminous die plate as working electrode, platinum or graphite as
To electrode, saturated calomel electrode as reference electrode, it is placed in electrodeposit liquid and utilizes three-electrode system in the hole of foraminous die plate
Middle position activity metal oxide obtains activation template；
4) prepare organic liquor, using activate template as anode, using platinum or graphite as cathode, using organic liquor as electrolyte,
It is electrolysed using Anodic Stripping principle, grows villiform nanostructure in activation template surface to get presoma is arrived；
5) presoma is placed in protective atmosphere and is calcined, surface can be obtained and be deposited with active metal and carbon and form nanometer
The copper current collector of structure.
Wherein, the specific preparation parameter of Examples 1 to 5 is as shown in following table table 1, table 2 and table 3.
1 specific preparation parameter (I) of table
2 specific preparation parameter (II) of table
3 specific preparation parameter (III) of table
Wherein, three-dimensional manometer copper oxide (pre- matrix) obtained in 2 preparation process of embodiment SEM figure as shown in Figure 1,
The SEM of further resulting three-dimensional manometer Copper substrate (foraminous die plate) schemes the villus as shown in Fig. 2, on final product copper current collector
Shape nanostructure is as shown in Figure 3.
From Fig. 1, Fig. 2 and Fig. 3 it will be evident that Copper substrate obtained by the method for the present invention and final product copper current collector
All have high specific surface area and complicated Specific surface area.
Titanium material obtained by Examples 1 to 5 is detected.By ethylene carbonate and ethylene carbonate with volume ratio 1:
1 volume ratio is configured to base fluid, lithium hexafluoro phosphate is dissolved in base fluid, electrolyte is made, in above-mentioned electrolyte: lithium hexafluoro phosphate
Molar concentration be 1 mol/L；Exist using titanium material obtained by prepared electrolyte, embodiment and polyethylene diagrams as material
CR2025 button cell is assembled into glove box equipped with argon gas to get lithium ion battery is arrived.The lithium-ion electric that will be prepared
Pond carries out loop test.Test capacity, coulombic efficiency and stable cycle-index of the battery under the current density of 500 mA/g.
Testing result is as shown in following table table 4.
4 testing result of table
From upper table table 3 it will be evident that copper current collector obtained by the present invention has extremely excellent chemical property,
There is outstanding performance in various aspects such as battery capacity, coulombic efficiency and stable cycle-indexes.
Claims (7)
1. a kind of method of copper current collector making Nano surface, which is characterized in that the described method comprises the following steps:
1) alkalies is configured, will be placed in alkalies by pretreated Copper substrate and erode processing, to it after erosion
It is dried, obtains pre- matrix；
2) using pre- matrix as working electrode, platinum or graphite as, as reference electrode, being placed in electricity to electrode, saturated calomel electrode
It solves in liquid and restores pre- matrix using three-electrode system, form foraminous die plate；
3) electrodeposit liquid containing active metallic ion is prepared, using foraminous die plate as working electrode, platinum or graphite as to electricity
Pole, saturated calomel electrode are placed in electrodeposit liquid and are sunk in the hole of foraminous die plate using three-electrode system as reference electrode
Product reactive metal oxides obtain activation template；
4) prepare organic liquor, using activate template as anode, using platinum or graphite as cathode, using organic liquor as electrolyte, utilization
Anodic Stripping principle is electrolysed, and grows villiform nanostructure in activation template surface to get presoma is arrived；
5) presoma is placed in protective atmosphere and is calcined, surface can be obtained and be deposited with active metal and carbon and form nanostructure
Copper current collector；
Wherein:
Alkalies described in step 1) is formulated by strong oxidizer, highly basic and water, wherein the concentration of strong oxidizer be 0.05~
2mol/L, the concentration of highly basic are 1~5mol/L；
The preparation method of electrodeposit liquid described in step 3) are as follows: the sulfate containing active metallic ion is soluble in water, highly basic is added
And stir, it is electrodeposit liquid that supernatant is then taken after 10~14h of standing；Wherein, sulfate concentration is 0.05~2mol/L, by force
Alkali concentration is 1~5mol/L, and the active metallic ion includes iron ion, zinc ion, titanium ion, nickel ion or cobalt ions；
Organic liquor described in step 4) is the DMF solution containing 0.2~0.8mol/L isonicotinic acid.
2. a kind of method of copper current collector making Nano surface according to claim 1, which is characterized in that done described in step 1)
Dry treatment temperature is 150~250 DEG C, the time is 1~3h；The strong oxidizer includes potassium peroxydisulfate, potassium bichromate or permanganic acid
Potassium.
3. a kind of method of copper current collector making Nano surface according to claim 1, which is characterized in that electricity described in step 2
Solve the aqueous sodium persulfate solution of potassium sulfate or 0.5~2mol/L that liquid is 0.5~2mol/L.
4. a kind of method of copper current collector making Nano surface according to claim 1 or 3, which is characterized in that step 2 institute
Reduction potential is -0.1~-3V when stating reduction, and the recovery time is 100~1000s.
5. a kind of method of copper current collector making Nano surface according to claim 1, which is characterized in that electricity described in step 3)
Sedimentary condition are as follows: electro-deposition electric current is -5~-20mA/cm2, electrodeposition time be 20~100s.
6. a kind of method of copper current collector making Nano surface according to claim 1, which is characterized in that electricity described in step 4)
The condition of solution are as follows: decomposition voltage is 3.0~4.5V, 15~20min of time.
7. a kind of method of copper current collector making Nano surface according to claim 1, which is characterized in that forged described in step 5)
Calcination temperature is 600~800 DEG C during burning, calcination time is 2~5h.
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